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Publication numberUS5532317 A
Publication typeGrant
Application numberUS 08/433,020
Publication dateJul 2, 1996
Filing dateMay 3, 1995
Priority dateMay 27, 1994
Fee statusPaid
Also published asCN1062577C, CN1126734A, DE69512566D1, DE69512566T2, EP0684282A1, EP0684282B1
Publication number08433020, 433020, US 5532317 A, US 5532317A, US-A-5532317, US5532317 A, US5532317A
InventorsTetsuya Shinmura, Kunihiko Konishi
Original AssigneeDenki Kagaku Kogyo Kabushiki Kaisha
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Process for producing a maleimide-modified heat-resistant abs resin
US 5532317 A
Abstract
A process for producing a maleimide-modified heat-resistant ABS resin comprising a maleimide copolymer, an ABS graft copolymer and an AS copolymer, which comprises kneading a maleimide copolymer, an ABS graft copolymer and optionally an AS copolymer to obtain a heat-resistant master batch resin, and further kneading an ABS graft copolymer and an AS copolymer to the heat-resistant master batch resin or kneading a resin composed of an ABS graft copolymer and an AS copolymer, to the heat-resistant master batch resin.
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Claims(14)
What is claimed is:
1. A process for producing a maleimide-modified heat resistant ABS resin comprising a maleimide copolymer, an ABS graft copolymer component consisting of one or more ABS graft copolymers, and an AS copolymer component consisting of one or more AS copolymers, which comprises kneading the maleimide copolymer, part of the ABS graft copolymer component and none or part of the AS copolymer component to obtain a heat-resistant master batch resin, and further (2a) kneading the remaining ABS graft copolymer component and all or the remaining AS copolymer component to the heat-resistant master batch resin or (2b) kneading a resin composed of the remaining ABS graft copolymer component and all or the remaining AS copolymer component, to the heat-resistant master batch resin.
2. The process for producing a maleimide-modified heat-resistant ABS resin according to claim 1, wherein from 50 to 75 wt % of the maleimide copolymer, from 25 to 50 wt % of the ABS graft copolymer and from 0 to 20 wt % of the AS copolymer are kneaded to obtain the heat-resistant master batch resin, and from 30 to 95 wt % in total of the ABS graft copolymer and the AS copolymer are further kneaded to from 5 to 70 wt % of the heat-resistant master batch resin.
3. The process for process for producing a maleimide-modified heat-resistant ABS resin according to claim 1, wherein the maleimide copolymer is a copolymer comprising from 40 to 70 wt % of an aromatic vinyl monomer unit, from 30 to 60 wt % of an unsaturated dicarboxylic acid imide derivative unit and from 0 to 20 wt % of the copolymerizable vinyl monomer unit.
4. The process for producing a maleimide-modified heat-resistant ABS resin according to claim 1, wherein the maleimide copolymer is a copolymer comprising from 45 to 65 wt % of an aromatic vinyl monomer unit, from 35 to 55 wt % of an unsaturated dicarboxylic acid imide derivative unit and from 0 to 15 wt % of other copolymerizable vinyl monomer unit.
5. The process for producing a maleimide-modified heat-resistant ABS resin according to claim i, wherein the maleimide copolymer comprises a styrene monomer unit and an N-phenyl maleimide monomer unit, or a styrene monomer unit, an N-phenyl maleimide monomer unit and an acrylonitrile monomer unit, or a styrene monomer unit, an N-phenylmaleimide monomer unit and a maleic anhydride monomer unit.
6. The process for producing a maleimide-modified heat-resistant ABS resin according to claim 1, wherein the ABS graft copolymer is a graft copolymer obtained by graft-copolymerizing from 30 to 70 parts by weight of a monomer mixture comprising from 65 to 70 wt % of an aromatic vinyl monomer, from 20 to 35 wt % of a vinyl cyanide monomer and from 0 to 10 wt % of other copolymerizable vinyl monomer, in the presence of from 30 to 70 parts by weight of a rubber polymer.
7. The process for producing a maleimide-modified heat-resistant ABS resin according to claim 6, wherein the rubber polymer is a butadiene polymer, and the aromatic vinyl monomer is a styrene monomer, and the vinyl cyanide monomer is acrylonitrile.
8. The process for producing a maleimide-modified heat-resistant ABS resin according to claim 1 or 2, wherein the ABS graft copolymer is a graft copolymer obtained by graft-copolymerizing from 40 to 60 parts by weight of a monomer mixture comprising from 70 to 75 wt % of an aromatic vinyl monomer, from 25 to 30 wt % of a vinyl cyanide monomer and from 0 to 10 wt % of other copolymerizable vinyl monomer, in the presence of from 40 to 60 parts by weight of a rubber polymer.
9. The process for producing a maleimide-modified heat-resistant ABS resin according to claim 1, wherein the ABS graft copolymer is a graft copolymer obtained by copolymerizing a monomer mixture comprising a styrene monomer and an acrylonitrile monomer, in a butadiene polymer.
10. The process for producing a maleimide-modified heat-resistant ABS resin according to claim 1, wherein the AS copolymer is a copolymer comprising from 65 to 80 wt % of an aromatic vinyl monomer, from 20 to 35 wt % of a vinyl cyanide monomer and from 0 to 10 wt % of other copolymerizable monomer.
11. The process for producing a maleimide-modified heat-resistant ABS resin according to claim 10, wherein the aromatic vinyl monomer is styrene and/or α-methylstyrene, and the vinyl cyanide monomer is an acrylonitrile.
12. The process for producing a maleimide-modified heat-resistant ABS resin according to claim 1, wherein the AS copolymer is a copolymer comprising from 68 to 78 wt % of an aromatic vinyl monomer, from 22 to 32 wt % of a vinyl cyanide monomer and from 0 to 10 wt % of other copolymerizable vinyl monomer.
13. The process for producing a maleimide-modified heat-resistant ABS resin according to claim 1, wherein the AS copolymer is a copolymer comprising a styrene monomer unit and an acrylonitrile monomer unit, or a styrene monomer unit, α-methylstyrene monomer unit and an acrylonitrile monomer unit.
14. A maleimide-modified heat-resistant ABS resin made by the process of claim 1.
Description

The present invention relates to a process for producing a maleimide-modified heat-resistant ABS resin. By employing the process of the present invention, it is possible to obtain a maleimide-modified heat-resistant ABS resin excellent in falling weight impact strength, and it is possible to reduce the wall thickness of a molded product as compared with a maleimide modified heat-resistant ABS resin obtained by a conventional process. Accordingly, the maleimide-modified heat-resistant resistant ABS resin prepared by the process of the present invention can be applied to various fields including fields of automobile parts, electric or electronic parts, household electric parts and sundries.

Heretofore, it has been common for the preparation of a maleimide-modified heat-resistant ABS resin to knead a maleimide copolymer, an ABS graft copolymer and an AS copolymer all at once to obtain a maleimide-modified heat-resistant ABS resin. However, such a conventional process has a drawback that no adequate falling weight impact strength can thereby be obtained, and particularly when a pigment is added, the falling weight impact strength deteriorates substantially.

It is an object of the present invention to provide a process for producing a maleimide-modified heat-resistant ABS resin which has high falling weight impact strength and which undergoes no substantial deterioration in the falling weight impact strength even when a pigment is incorporated.

The present invention provides a process for producing a maleimide-modified heat-resistant ABS resin comprising a maleimide copolymer, an ABS graft copolymer and an AS copolymer, which comprises kneading a maleimide copolymer, an ABS graft copolymer and optionally an AS copolymer to obtain a heat-resistant master batch resin, and further kneading an ABS graft copolymer and an AS copolymer to the heat-resistant master batch resin or kneading a resin composed of an ABS graft copolymer and an AS copolymer, to the heat-resistant master batch resin, whereby it is possible to obtain a maleimide-modified heat-resistant ABS resin which has high falling weight impact strength and which is less susceptible to deterioration in falling weight impact strength even when a pigment is incorporated.

Now, the present invention will be described in detail with reference to the preferred embodiments.

Firstly, the maleimide copolymer which may be used in the present invention, will be described.

As a first method, the maleimide Copolymer can be obtained by a method of copolymerizing a mixture comprising an aromatic vinyl monomer, an unsaturated dicarboxylic acid imide derivative and a vinyl monomer copolymerizable therewith.

As a second method, a method may be mentioned which comprises copolymerizing a mixture comprising an aromatic vinyl monomer, an unsaturated dicarboxylic acid anhydride and a vinyl monomer copolymerizable therewith, and then reacting ammonia and/or a primary amine thereto to convert the acid anhydride groups to imide groups.

By either method, the maleimide copolymer can be obtained.

The aromatic vinyl monomer may be a styrene monomer or its substituted monomer, such as styrene, α-methylstyrene, vinyl toluene, p-methylstyrene, t-butylstyrene or chlorostyrene. Among them, styrene is particularly preferred.

The unsaturated dicarboxylic acid imide derivative may, for example, be maleimide, or a maleimide derivative, for example, an N-alkylmaleimide such as N-methylmaleimide, N-butylmaleimide or N-cyclohexylmaleimide, or an N-arylmaleimide wherein the aryl group may, for example, be phenyl, chlorophenyl, methylphenyl, methoxyphenyl or tribromophenyl. Such derivatives may be used in combination as a mixture of two or more of them. Among them, N-phenylmaleimide is particularly preferred.

The unsaturated dicarboxylic acid anhydride which is used in the second method, may, for example, be maleic anhydride.

The vinyl monomer copolymerizable therewith may, for example, be a vinyl cyanide monomer such as acrylonitrile or methacrylonitrile, an acrylic acid ester monomer such as methyl acrylate or ethyl acrylate, a methacrylic acid ester monomer such as methyl methacrylate or ethyl methacrylate, a vinyl carboxylic acid monomer such as acrylic acid or methacrylic acid, acrylic acid amide, or methacrylic acid amide. Further, in the first method, maleic anhydride may also be mentioned. In the second method, maleic anhydride groups remained as not converted to maleimide groups, may be incorporated in the copolymer.

The ammonia or the primary amine to be used in the second method may be in an anhydrous state or in the form of an aqueous solution. The primary amine may, for example, be an alkylamine such as methylamine, ethylamine, butylamine or cyclohexylamine,i or an aromatic amine such as aniline, toluidine, chloroaniline, methoxyaniline or tribromoaniline. Among them, aniline is particularly preferred.

For the first method, any one of conventional polymerization methods such as suspension polymerization, emulsion polymerization, solution polymerization or bulk polymerization, may be employed. For the second method, bulk-suspension polymerization, solution polymerization or bulk polymerization may, for example, be suitably employed.

The maleimide copolymer is a copolymer comprising from 40 to 70 wt % of an aromatic vinyl monomer unit, from 30 to 60 wt % of an unsaturated dicarboxylic acid imide derivative unit and from 0 to 20 wt % of other copolymerizable vinyl monomer unit. If the composition is outside these ranges, the compatibility with other components tends to be poor, whereby the falling weight impact strength is likely to be low. More preferably, the copolymer comprises from 45 to 65 wt % of an aromatic vinyl monomer unit, from 35 to 55 wt % of an unsaturated dicarboxylic acid imide derivative unit and from 0 to 15 wt % of other copolymerizable vinyl monomer unit.

Now, the ABS graft copolymer will be described.

The ABS graft copolymer is a graft copolymer obtained by copolymerizing a monomer mixture comprising an aromatic vinyl monomer, a vinyl cyanide monomer and other copolymerizable vinyl monomer, in the presence of a rubber-like polymer.

The rubber-like polymer may, for example, be a butadiene polymer, a butadiene-styrene copolymer, an ethylene-propylene copolymer, an ethylene-propylene-diene copolymer, or an acrylic acid ester copolymer.

The aromatic vinyl monomer may be the same monomer as the aromatic vinyl monomer used in the above method for producing the maleimide copolymer. Styrene is particularly preferred.

The vinyl cyanide monomer may, for example, be acrylonitrile or methacrylonitrile, and acrylonitrile is particularly preferred.

As other copolymerizable vinyl monomer, the same monomer as said other copolymerizable vinyl monomer used in the above method for producing the maleimide copolymer, or an unsaturated dicarboxylic acid imide derivative, may be employed.

The ABS graft copolymer can be obtained by graft-copolymerizing from 30 to 70 parts by weight of a monomer mixture comprising from 65 to 80 wt % of the aromatic vinyl monomer, from 20 to 35 wt % of the Vinyl cyanide monomer and from 0 to 10 wt % of other copolymerizable vinyl monomer, in the presence of from 30 to 70 parts by weight of the rubber-like polymer. If the composition is outside these ranges, the compatibility with other components tends to be poor, whereby the falling weight impact strength is likely to be low. More preferably, the copolymer is obtained by graft-copolymerizing from 40 to 60 parts by weight of a monomer mixture comprising from 70 to 75 wt % of the aromatic vinyl monomer, from 25 to 30 wt % of the vinyl cyanide monomer and from 0 to 10 wt % of other copolymerizable vinyl monomer, in the presence of from 40 to 60 parts by weight of the rubber-like polymer.

In graft polymerization, it is usually difficult to graft the entire amount of monomers to a rubber-like polymer, and a non-grafted copolymer will be produced as a by-product. In the present inventions, the graft copolymer may be a pure graft copolymer having such a non-grafted copolymer positively separated and removed, or may be a graft polymer which contains such a non-grafted copolymer.

For the graft polymerization, any conventional polymerization technique may be employed. For example, an aqueous non-homogenous polymerization such as suspension polymerization or emulsion polymerization, bulk polymerization, solution polymerization or a precipitation polymerization in a poor solvent for the resulting polymer, may be mentioned. Emulsion polymerization is preferred from the viewpoint that the rubber particle size which is influential over the strength., can easily be controlled.

Now, the AS copolymer will be described.

The AS copolymer is a copolymer comprising an aromatic vinyl monomer unit, a vinyl cyanide monomer unit and other copolymerizable vinyl monomer unit.

The aromatic vinyl monomer may be the Same monomer as the aromatic vinyl monomer used in the above-mentioned method for preparing the maleimide copolymer. Among such monomers, styrene or α-methylstyrene is particularly preferred.

The vinyl cyanide monomer may, for example, be acrylonitrile or methacrylonitrile, and acrylonitrile is particularly preferred.

As other copolymerizable vinyl monomer, the same monomer as said other copolymerizable vinyl monomer used in the above-mentioned method for preparing the maleimide copolymer, may be employed.

The AS copolymer is a copolymer comprising from 65 to 80 wt % of the aromatic vinyl monomer, from 6m 20 to 35 wt of the vinyl cyanide monomer and from 0 to 10 wt % of other copolymerizable vinyl monomer. If the composition is outside these ranges, the compatibility with other components tends to be poor, whereby the falling weight impact strength is likely to be low. More preferably, it is a copolymer comprising from 68 to 78 wt % of the aromatic vinyl monomer, from 22 to 32 wt % of the vinyl cyanide monomer and from 0 to 10 wt % of other copolymerizable vinyl monomer.

The AS copolymer can be produced by a conventional polymerization method. For example, a polymerization method such as suspension polymerization, solution polymerization or emulsion polymerization may be employed.

The feature of the process for producing a maleimide-modified heat-resistant ABS resin of the present invention resides in that a maleimide-modified heat-resistant ABS resin having high falling weight impact strength is obtained by kneading the ABS graft copolymer and the AS copolymer or kneading a resign comprising the ABS graft copolymer and the AS copolymer, to a heat-resistant resistant master batch resin prepared by kneading the maleimide copolymer, the ABS graft copolymer and optionally the AS copolymer.

The composition of the heat-resistant master batch resin is preferably from 50 to 75 wt % of the maleimide copolymer, from 25 to 50 wt % of the ABS graft copolymer and from 0 to 20 wt % of the AS copolymer. If the composition is outside these ranges, the falling weight impact strength or the heat resistance of the finally obtainable maleimide-modified heat-resistant ABS resin tends to be low.

The blend ratio of the heat-resistant master batch resin, and the ABS graft copolymer and the AS copolymer, is preferably from 5 to 70 wt % of the heat-resistant master batch resin and from 30 to 95 wt % in total of the ABS graft copolymer and the AS copolymer. If the amount of the heat-resistant master batch resin iS less than 5 wt %, the effect for improving the heat resistance tends to be poor, and if it exceeds 70 wt %, the effect for preventing, deterioration in the falling weight impact strength can not be obtained even by the process of the present invention.

As a means for 6r kneading, a single screw extruder or a twin screw extruder can suitably be employed. For preliminary blending prior to kneading by an extruder, a conventional apparatus such as a Henschel mixer or a tumbler mixer may be employed.

To the heat-resistant master batch resin or the maleimide-modified heat-resistant ABS resin obtained by the process of the present invention, an antioxidant, an ultraviolet absorber, a coloring agent, a plasticizer, a lubricant, a flame retardant, glass fibers, carbon fibers, calcium carbonate, talc or mica, may, for example, be incorporated as the case requires.

Now, the present invention will be described in further detail with reference to Examples. However, it should be understood that the present invention is by no means restricted by such specific Examples. In the Examples, "parts" and "%" mean "parts by weight" and "% by weight", respectively.

Starting material resins

Used as the maleimide copolymer was a copolymer (SMI-1) of styrene/N-phenylmaleimide=50/50 having a weight average molecular weight of 182,000, a copolymer (SMI-2) of styrene/N-phenylmaleimide/acrylonitriles=50/35/15 having a weight average molecular weight of 165,000, or a copolymer (SMI-3) of styrene/N-phenylmaleimide/maleic anhydride=47/51/2 having a weight average molecular weight of 164,000.

Used as the ABS graft copolymer was a graft copolymer (GF) comprising 50% of butadiene rubber 37% of styrene and 13% of acrylonitrile having a graft ratio of 40% and a weight average molecular weight of the non-grafted copolymer of 84,000.

Used as the AS copolymer was a copolymer (AS) of styrene/acrylonitrile=75/25 having a Weight average molecular weight of 128,000.

Further, as the resin comprising an ABS graft copolymer and an AS copolymer, commercially available ABS resin "Denka GR-2000 (manufactured by Denki Kagaku Kogyo K. K.)" was used.

EXAMPLES 1 TO 10

(1) Preparation of heat-resistant master batch resin

Kneading for preparing the heat-resistant master batch resin was carried out by means of a twin screw extruder TEM-35B manufactured by Toshiba Kikai K. K. (diameter of screw: 37 mm, L/D=32) at a cylinder temperature of 280 C., a screw rotational speed of 200 rpm and a starting material feeding rate of 20/kg/hr. The compositions of the heat-resistant master batch resins thus prepared are shown in Table 1. The prepared master batch resins were referred to as MB-1 to MB-6, respectively.

              TABLE 1______________________________________Compositions of heat-resistant master batch resins(parts by weight)Startingmaterials    MB-1    MB-2    MB-3  MB-4  MB-5  MB-6______________________________________SMI-1    60                    50    60    60SMI-2            70SMI-3                    60GF       40      30      40    30    40    40AS                             10Carbon black                          2Titanium                                    4oxide______________________________________

(2) Preparation of maleimide-modified heat-resistant ABS resin

Kneading for preparing the maleimide-modified heat-resistant ABS resin was carried out by means of a single screw extruder NVC-65 manufactured by Nakatani Kikai K. K. (diameter of screw: 65 mm, L/D=32) at a cylinder temperature of 260 C. at a screw rotational speed of 100 rpm and with a lap distance for adjusting the kneading degree being 10 mm. The discharge rate was about 100 kg/hr.

The compositions of the maleimide-modified heat-resistant ABS resins prepared in accordance with the method of the present invention and their physical properties are shown in Tables 2 and 3 as Examples 1 to 10.

                                  TABLE 2__________________________________________________________________________Examples 1 to 5 (Blend proportions are parts by weight)Starting materials      Example 1            Example 2                  Example 3                        Example 4                              Example 5__________________________________________________________________________MB-1       25                      25MB-2             25MB-3                   25MB-4                         25GF         30    30    30    30    30AS         45    45    45    45    45Titanium oxide                      2Falling weightimpact strength(cm)2 mm       140   130   130   130   120thickness1.5 mm     60    50    60    60    50thickVicat softening point      111   108   113   112   112(C.)__________________________________________________________________________

                                  TABLE 3__________________________________________________________________________Examples 6 to 10 (Blend proportions are parts by weight)Starting materials      Example 6            Example 7                  Example 8                        Example 9                              Example 10__________________________________________________________________________MB-1                   15    25MB-3                               50MB-5       25MB-6             25GF         30    30AS         45    45GR-2000                85    75    50Titanium oxide          2     2     2Falling weightimpact strength(cm)2 mm       130   130   140   130   60thickness1.5 mm     60    60    80    50    20thickVicat softening point      111   111   107   112   124(C.)__________________________________________________________________________
COMPARATIVE EXAMPLES 1 TO 5

The physical properties of the maleimide-modified heat-resistant ABS resins prepared by a conventional process are shown in Table 4 as Comparative Example 1 which corresponds to Example 1, Comparative Example 2 which corresponds to Example 5, Comparative Example 3 which corresponds to Example 6, Comparative Example 4 which corresponds to Example 7 and Comparative Example 5 which corresponds to Example 10. In these Comparative Examples, kneading was carried out by means of a twin screw extruder TEM-35B under the same conditions as for the preparation of the heat-resistant master batch resin.

                                  TABLE 4__________________________________________________________________________Comparative Examples 1 to 5 (Blend proportions are parts by weight)      Comparative             Comparative                    Comparative                           Comparative                                  ComparativeStarting materials      Example 1             Example 2                    Example 3                           Example 4                                  Example 5__________________________________________________________________________SMI-1      15     15     15     15SMI-3                                  30GF         40     40     40     40     38AS         45     45     45     45     32Carbon black             0.5Titanium oxide     2             1      2Falling weightimpact strength(cm)2 mm       120    90     100    100    20thickness1.5 mm     50     30     30     20     <10thickVicat softening point      111    112    111    111    123(C.)__________________________________________________________________________

Test specimens for measuring the physical properties were prepared by injection molding. The conditions for measuring the physical properties were as follows.

(a) Falling weight impact strength: In accordance with JIS K7211, the height at 50% breakage was measured. The test specimen was a square plate of 90 mm90 mma thickness of 2 mm or 1.5 mm. The measuring temperature was 23 C., and the measuring humidity was 50% RH. The weight was 1 kg in the case of the square plate having a thickness of 2 mm or 500 g in the case of the square plate having a thickness of 1.5 mm. In each case, the forward end of the weight had 4.75 mmR.

(b) Vicat softening point: In accordance with JIS K7206, the Vicat softening point was measured under a load of 5 kg at a temperature raising rate of 50 C./hr using a test specimen of 1/4 inch.

When Example 1 wherein no pigment was incorporated, is compared with Examples 5 and 7 wherein titanium oxide was incorporated and with Example 6 wherein carbon black was incorporated, no substantial deterioration is observed in the falling weight impact strength. Thus, it is evident that according to the process of the present invention, it is possible to prevent deterioration of the falling weight impact strength due to incorporation of a pigment.

When Example 1 is compared with Comparative Example 1, it is evident that even in a case where no pigment is incorporated, the falling weight impact strength of the maleimide-modified heat-resistant ABS resin prepared by the process of the present invention is higher.

Likewise, from the comparison between Example 5 and Comparative Example 2, between Example 6 and Comparative Example 3, between Example 7 and Comparative Example 4 and between Example 10 and Comparative Example 5, it is evident that according to the process of the present invention, it is possible to prevent deterioration in the falling weight impact strength of the maleimide-modified heat-resistant ABS resin in a case where a pigment is incorporated.

COMPARATIVE EXAMPLE 6

Comparative Example 6 will be described. To the maleimide-modified heat-resistant ABS resin prepared in Comparative Example 1, 2 parts of titanium oxide was incorporated, and the mixture was kneaded by a single screw extruder NVC-65. From the obtained pellets, a test specimen was prepared by injection molding, and its physical properties were measured. As a result, the Vicat softening point was 112 C. Further, the falling weight impact strength of a square plate having a thickness of 2 mm was 80 cm, and the falling weight impact strength of a square plate having a thickness of 1.5 mm was 20 cm.

From Comparative Example 6, it is evident that the effects of the present invention are not simply due to an increase number of kneading operation.

The maleimide-modified heat-resistant ABS resin obtained by the process of the present invention is excellent in the falling weight impact strength, which is an index of practical strength, whereby the wall thickness of a molded product can be reduced as compared with a maleimide-modified heat-resistant ABS resin obtained by a conventional process. Accordingly, it is possible to reduce the cost, and such a resin can be applied to various fields including fields of automobile parts, electric or electronic parts, household electric parts and sundries.

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US4404322 *Jan 20, 1982Sep 13, 1983Denki Kagaku Kogyo Kabushiki KaishaHeat resistant resin composition
US4668738 *Dec 24, 1985May 26, 1987The Dow Chemical CompanyProcess for promoting syneresis in high rubber ABS latex
US4829125 *May 23, 1988May 9, 1989Lucky Ltd.Blending crystalline polypropylene with its preblend with olefin copolymer
US4994515 *Jun 27, 1989Feb 19, 1991Showa Denko Kabushiki KaishaHeat-resistant resin composition
US5100947 *Mar 19, 1990Mar 31, 1992Advanced Elastomer Systems, L. P.Dynamically vulcanized alloys having improved stiffness/impact balance
EP0134519A2 *Jul 18, 1984Mar 20, 1985Denki Kagaku Kogyo Kabushiki KaishaThermoplastic resin composition
EP0202615A1 *May 15, 1986Nov 26, 1986Mitsubishi Kasei Polytec CompanyThermoplastic resin composition having heat and impact resistant properties
EP0587907A1 *Mar 30, 1993Mar 23, 1994Sumitomo Dow LimitedThermoplastic resin composition containing glass fiber
FR2329705A1 * Title not available
JPH0220528A * Title not available
Referenced by
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US6133354 *Nov 17, 1998Oct 17, 2000Bridgestone CorporationMixing a poly(dialkylsubstituted ethylene-co-maleimide) polymer such as polyisobutylene-co-maleimide, and plasticizers or extenders within a non-vulcanized thermoplastic elastomer to form a damping gel; tensile strength and tear strength
US6184292Oct 5, 1998Feb 6, 2001Bridgestone CorporationSoft gel polymers for high temperature use
US6191217Nov 17, 1998Feb 20, 2001Bridgestone CorporationGels derived from polypropylene grafted alkyl vinylether-maleimide copolymers
US6204354May 6, 1998Mar 20, 2001Bridgestone CorporationSoft compounds derived from polypropylene grafted disubstituted ethylene- maleimide copolymers
US6207763Jun 12, 1998Mar 27, 2001Bridgestone CorporationA copolymer of substituted or unsubstituted 1-20 alkyl group disubstituted ethylene-maleimide copolymer(a reaction product of disubtituted ethylene-maleic anhydride imidized with primary amine) is a plasticizer for rubber; high damping
US6248825May 6, 1998Jun 19, 2001Bridgestone CorporationPoly(alkenylbenzene-maleimide)
US6248827 *Dec 22, 1997Jun 19, 2001Bridgestone CorporationCured elastomer
US6350800Jun 5, 2000Feb 26, 2002Bridgestone CorporationSoft polymer gel
US6353054Jul 31, 2000Mar 5, 2002Bridgestone CorporationAlkenyl-co-maleimide/diene rubber copolymers and applications
US6359064Sep 8, 2000Mar 19, 2002Bridgestone CorporationCombining poly(alkenyl-co-maleimide), maleated polyalkylene and crosslinking agent; reacting to crosslink and to form a maleated polyalkylene grafted poly(alkenyl-co-maleimide); combining with with a polyester to provide the elastomer
US6369166Sep 29, 2000Apr 9, 2002Bridgestone CorporationPlasticized; tensile and tear strength; elongation; high damping; ethylene-maleic anhydride copolymer reacted with primary amine
US6384134Jun 5, 2000May 7, 2002Bridgestone CorporationPolymer gel composition comprising maleated polyalkylene grated via grafting agent to poly(alkenyl-co-maleimide), epoxy polymer, and optionally, extender; vibration damping material
US6417259Jun 5, 2000Jul 9, 2002Bridgestone CorporationPolyalkylene grafted centipede polymers
US6455626Jun 5, 2001Sep 24, 2002Bridgestone CorporationGels derived from extending grafted centipede polymers and polypropylene
US6476117Jun 5, 2000Nov 5, 2002Bridgestone CorporationGrafted near-gelation polymers having high damping properties
US6599988Apr 29, 2002Jul 29, 2003Bridgestone CorporationMaleimide and styrene copolymer; tensile strength, elongation, tear strength
US20100168333 *Dec 28, 2009Jul 1, 2010Cheil Industries Inc.Thermoplastic Resin Having Excellent Heat Resistance and Impact Strength and Method of Preparing the Same
Classifications
U.S. Classification525/73, 525/71
International ClassificationC08L55/00, C08L51/04, C08L55/02, C08L33/24, C08L35/06, C08L25/08, C08L25/12
Cooperative ClassificationC08L55/02, C08L25/12, C08L25/08, C08L33/24
European ClassificationC08L25/12, C08L55/02
Legal Events
DateCodeEventDescription
Dec 11, 2007FPAYFee payment
Year of fee payment: 12
Dec 9, 2003FPAYFee payment
Year of fee payment: 8
Dec 29, 1999FPAYFee payment
Year of fee payment: 4
May 3, 1995ASAssignment
Owner name: DENKI KAGAKU KOGYO KABUSHIKI KAISHA, JAPAN
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:SHINMURA, TETSUYA;KONISHI, KUNIHIKO;REEL/FRAME:007514/0997
Effective date: 19950420